WO2017175600A1 - Membrane semi-perméable - Google Patents

Membrane semi-perméable Download PDF

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Publication number
WO2017175600A1
WO2017175600A1 PCT/JP2017/011922 JP2017011922W WO2017175600A1 WO 2017175600 A1 WO2017175600 A1 WO 2017175600A1 JP 2017011922 W JP2017011922 W JP 2017011922W WO 2017175600 A1 WO2017175600 A1 WO 2017175600A1
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WIPO (PCT)
Prior art keywords
group
cellulose
membrane
cellulose ester
semipermeable membrane
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PCT/JP2017/011922
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English (en)
Japanese (ja)
Inventor
橋爪知弘
松村裕之
柴田徹
大野充
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株式会社ダイセル
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Priority to EP17778979.9A priority Critical patent/EP3441133B1/fr
Priority to CN201780022383.4A priority patent/CN108883379B/zh
Priority to KR1020187028433A priority patent/KR102229836B1/ko
Priority to JP2018510298A priority patent/JP6981965B2/ja
Priority to US16/091,728 priority patent/US10926230B2/en
Publication of WO2017175600A1 publication Critical patent/WO2017175600A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002—Forward osmosis or direct osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002—Forward osmosis or direct osmosis
    • B01D61/0022—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/18—Mixed esters, e.g. cellulose acetate-butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
    • C08B3/10—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate with five or more carbon-atoms, e.g. valerate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/36—Introduction of specific chemical groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration

Definitions

  • the present invention relates to a semipermeable membrane that can be used for water treatment in various fields and has better chlorine resistance and alkali resistance than a cellulose triacetate membrane.
  • Japanese Patent No. 5471242 discloses an invention of a water treatment method using a chlorine-resistant RO membrane (paragraph number 0031) made of cellulose triacetate or the like.
  • Japanese Patent No. 5418739 discloses an invention of a hollow fiber type semipermeable membrane made of cellulose acetate for forward osmosis treatment.
  • Paragraph No. 0017 describes that cellulose triacetate is preferable in terms of durability and resistance to chlorine, which is a germicide.
  • Japanese Patent Application Laid-Open No. 10-52630 describes an invention of a method for producing a stable and storable cellulose dialysis membrane in the form of a flat membrane, tubular membrane or hollow fiber membrane for a low flux, medium flux or high flux range. Yes. The use of modified cellulose as a film-forming component is described. Summary of the Invention
  • An object of the present invention is to provide a semipermeable membrane made of a cellulose ester, which has higher chlorine resistance and alkali resistance than a cellulose triacetate membrane.
  • the present invention provides a semipermeable membrane comprising a cellulose ester, wherein the cellulose ester has a benzoyl group which may have a substituent.
  • the semipermeable membrane of the present invention has higher chlorine resistance and alkali resistance than the cellulose triacetate membrane.
  • FIG. 3 is an explanatory diagram of a method for producing a porous filament in Example 1.
  • the semipermeable membrane of the present invention comprises a cellulose ester, and the cellulose ester has a benzoyl group which may have a substituent.
  • the benzoyl group which may have a substituent is a benzoyl group or an alkyl such as a methyl group, a trifluoromethyl group, a tert-butyl group or a phenyl group at one or more positions of the ortho position, meta position and para position.
  • One or more groups such as an alkoxy group such as a group, a methoxy group, and a phenoxy group, a hydroxy group, an amino group, an imino group, a carboxyl group, a sulfonic acid group, an acid group such as a salt thereof, a halogeno group, a cyano group, and a nitro group
  • the degree of substitution of the benzoyl group which may have a substituent is preferably in the range of 0.5 to 3.0 in order to increase the chlorine resistance and alkali resistance of the hollow fiber membrane, and 1.0 to 3.0 Is more preferable, the range of 1.5 to 3.0 is still more preferable, the range of 2.0 to 3.0 is still more preferable, and the range of 2.5 to 3.0 is still more preferable.
  • the degree of substitution of each substituent of the cellulose ester can be confirmed by 1 H-NMR and 13 C-NMR.
  • the other substituents are derived from fatty acids or fatty acid esters such as acetyl groups, propanoyl groups, butyroyl groups, etc. Groups, alkoxy groups such as methoxy group and ethoxy group, carboxymethyl group, hydroxyethyl group, hydroxypropyl group and the like.
  • the other substituent may be one kind of substituent or two or more kinds of substituents.
  • the degree of substitution of a benzoyl group which may have a substituent the degree of substitution of other substituents, and the degree of substitution corresponding to an unsubstituted hydroxy group (hydroxy group substitution degree)
  • the total value of is 3.0.
  • Cellulose ester may have an unsubstituted hydroxy group, but in order to increase the chlorine resistance of the hollow fiber membrane, it is preferable that the number of unsubstituted hydroxy groups is small, which corresponds to an unsubstituted hydroxy group.
  • the degree of substitution is preferably 1.5 or less, and more preferably 0.5 or less.
  • the cellulose ester preferably has a solubility parameter (Feedros method) of 21.5 to 25.0 (MPa) 0.5 , more preferably 22.5 to 25.0 (MPa) 0.5 .
  • the dissolution parameter was calculated by the calculation method of the dissolution parameter (Fedros method) by R. F. Ferors described in Polymer Engineering and Science, Vol. 14, No. 2, P.147-P.154.
  • the water solubility parameter is 47.9 (MPa) 0.5 .
  • Cellulose ester can use cellulose benzoate, cellulose acetate benzoate, cellulose propionate benzoate, cellulose butyrate benzoate, methyl cellulose benzoate, ethyl cellulose benzoate, etc., but water permeability, low fouling performance similar to cellulose triacetate membrane Therefore, cellulose benzoate and cellulose acetate benzoate are preferable.
  • the semipermeable membrane of the present invention is produced using a cellulose ester having a benzoyl group which may have a substituent, and the cellulose ester, a solvent, and salts if necessary, A film-forming solution containing a non-solvent can be used.
  • the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP).
  • Dimethyl sulfoxide (DMSO) is preferred.
  • the non-solvent include ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
  • the salts include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, and calcium chloride, with lithium chloride being preferred.
  • the concentration of the cellulose ester and the solvent is preferably 10 to 35% by mass of the cellulose ester and 65 to 90% by mass of the solvent.
  • the salt is preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the total mass of the cellulose ester and the solvent.
  • the semipermeable membrane of the present invention can be produced by using the above-mentioned membrane-forming solution and utilizing a known production method, for example, the production method described in Examples of Japanese Patent No. 5418739.
  • the semipermeable membrane of the present invention is preferably a separation membrane or a flat membrane of a hollow fiber membrane, a reverse osmosis membrane or a forward osmosis membrane.
  • Production Example 1 (Production of cellulose ester by saponification and benzoylation of cellulose diacetate)
  • a round bottom flask equipped with a stirrer and a condenser tube 900 g of an aqueous solution containing ammonia was added, and then 100 g of cellulose diacetate having an acetyl substitution degree of 2.44 was added and stirred at room temperature.
  • solids were collected by suction filtration to obtain a wet cake containing cellulose.
  • the obtained wet cake was put in 300 g of DMSO (N, N-dimethylsulfoxide), stirred for 1 hour at room temperature, and subjected to suction filtration again to collect a solid.
  • DMSO N, N-dimethylsulfoxide
  • the cellulose was added to a solution obtained by dissolving 56 g of lithium chloride in 460 g of DMAC (N, N-dimethylacetamide) and stirred at 100 ° C. to dissolve the cellulose.
  • the above cellulose solution was put into a round bottom flask equipped with a stirrer and a cooling tube, and stirring was started. While continuing stirring, an excessive amount of benzoyl chloride with respect to the hydroxy group of cellulose was dropped from the dropping funnel, and then the temperature was raised to 80 ° C. and stirring was continued. The resulting reaction mixture was cooled to room temperature and methanol was added with stirring to form a precipitate.
  • the precipitate was collected by suction filtration to obtain a crude cellulose benzoate wet cake. Ethanol was added to the obtained wet cake, and the mixture was washed by stirring and drained. This washing operation with ethanol was repeated three more times, and then the solvent was replaced with water. Cellulose tribenzoate was obtained by drying with a hot air dryer. The degree of substitution of the benzoyl group was 2.90. The degree of substitution was confirmed by 1 H-NMR and 13 C-NMR.
  • Production Example 6 In the same manner as in Production Example 1, after adding dropwise an excessive amount of benzoyl chloride, the temperature was raised to 80 ° C., and stirring was continued for a longer time than Production Example 1, whereby cellulose tribenzoate having a benzoyl group substitution degree of 3.00 was obtained. Obtained. The degree of substitution was confirmed by 1 H-NMR and 13 C-NMR.
  • the film forming method is as follows. Dissolve the film-forming solution sufficiently at 105 ° C, and discharge it at 80 ° C from the outside of the double saddle type spinneret. And the solvent was sufficiently removed in the washing tank.
  • the obtained hollow fiber membrane was stored in a wet state in which moisture was not dried, and each item shown in Table 2 was measured.
  • Test Example 1 Hollow Fiber Membrane Chlorine Resistance Test
  • a sodium hypochlorite aqueous solution having an effective chlorine concentration of 500 ppm was used as a test solution.
  • the effective chlorine concentration was measured using a handy water quality meter AQUAB manufactured by Shibata Kagaku, model AQ-102.
  • 50 hollow fiber membranes are soaked in a plastic container containing 1 L of 500 ppm sodium hypochlorite aqueous solution with a liquid temperature of about 25 ° C. as a test solution, and a new 500 ppm hypochlorous acid is added every 7 days.
  • aqueous sodium acid solution was prepared, and the entire test solution was replaced.
  • 10 hollow fibers were taken out from the plastic container every 7 days, washed with tap water, wiped off moisture, and measured for tensile strength and elongation while being moist.
  • Test Example 2 Measurement of “tensile strength” and “elongation” and judgment method of chlorine resistance) Using a small desktop tester (EZ-Test, manufactured by Shimadzu Corporation), measurements were carried out at a pulling speed of 20 mm / min by sandwiching one hollow fiber membrane at a time so that the distance between chucks was 5 cm. Based on the value of “tensile strength” of the hollow fiber membrane not immersed in the 500 ppm sodium hypochlorite aqueous solution, the time (number of days) when the value falls below 90% of the reference value was determined. In addition, by plotting the “tensile strength” of each measurement time and creating a calibration curve, the time (number of days) when it falls below 90% of the reference value was obtained. The “tensile strength” was an average value of 8 pieces excluding the highest value and the lowest value of “tensile strength” measured by 10 pieces of the same sample.
  • Test example 3 pure water permeability coefficient
  • pure water is supplied at 0.1 MPa from the other end side, and pure water that permeates from the hollow fiber membrane for a certain time
  • the volume of water was measured. This volume was divided by the sampling time (h) and the membrane area (m 2 ) on the inner surface of the hollow fiber membrane to obtain a pure water permeability coefficient [L / m 2 ⁇ h (0.1 MPa)].
  • the chlorine resistance of the hollow fiber membranes of Example 1 and Example 2 was 30 days and 70 days or more, respectively, and the chlorine resistance of the cellulose triacetate of Comparative Example 1 and the cellulose diacetate hollow fiber membrane of Comparative Example 2, It was much better than the 5th and 3rd respectively.
  • Reference example 1 Using the cellulose ester obtained in Production Example 1, a porous filament was spun using the apparatus shown in FIG. A predetermined amount of DMSO as a solvent was charged into a round bottom flask, and the cellulose ester was added at a mixing ratio shown in Table 3 while stirring with a three-one motor, and then heated in an oil bath to be completely dissolved. The cellulose ester solution (dope) was transferred to a sample bottle, allowed to cool to room temperature, and deaerated. Using a syringe pump 2 with a nozzle having a diameter of about 0.5 mm at the tip, using a syringe pump 2, it is discharged into a mug 4 containing 25 ° C.
  • the “tensile strength” was an average value of three samples excluding the highest value and the lowest value of the “tensile strength” measured on the same sample.
  • Reference Examples 2-6 In the same manner as in Reference Example 1, the cellulose esters obtained in Production Examples 2 to 6 were spun into porous filaments at the mixing ratio of the solvent and cellulose ester shown in Table 3, respectively. The diameters of the porous filaments of Reference Examples 2 to 6 were all 0.5 mm. The solvent of Production Examples 2 to 5 was spun with DMSO, and the solvent of Production Example 6 was spun with NMP. Using the obtained porous filament, chlorine resistance and alkali resistance were evaluated based on the value of “tensile strength” of the porous filament of each cellulose ester. The results are shown in Table 3.
  • Comparative Reference Examples 1 and 2 Using cellulose triacetate as comparative reference example 1 and cellulose diacetate (both manufactured by Daicel Corporation) as comparative reference example 2, the same as in reference example 1, the mixing ratio of DMSO solvent and cellulose ester described in Table 3, Porous filaments were spun (diameter 0.5 mm) and evaluated for chlorine resistance and alkali resistance. The results are shown in Table 3.
  • Comparative Reference Examples 3 and 4 Similarly to Comparative Reference Example 2, cellulose diacetate is used to react an excess amount of acid chloride with respect to the hydroxy group (Comparative Reference Example 3 is pentyl chloride, Comparative Example Reference Example 4 is cyclohexyl carboxylic acid chloride), and cellulose ester is reacted.
  • the porous filament was spun at a mixing ratio of DMSO solvent and cellulose ester described in Table 3 (diameter 0.5 mm) to evaluate chlorine resistance and alkali resistance. The results are shown in Table 3.
  • tensile strength” and “elongation” in each of Reference Examples 1 to 6 and Comparative Reference Examples 1 to 4 are the tensile strengths of porous filaments not immersed in an aqueous sodium hypochlorite solution or an aqueous alkali solution. And elongation.
  • the tendency of the measurement results of Reference Examples 1 to 6 and Comparative Reference Examples 1 to 4 for the porous filaments shown in Table 3 is the tendency of the measurement result of the hollow fiber membrane as it is.
  • the porous filaments of Reference Examples 2 to 6 were superior in chlorine resistance and alkali resistance when the degree of substitution of the benzoyl group was higher.
  • the chlorine resistance of the porous filaments of Comparative Reference Examples 3 and 4 was 19 days and 14 days, respectively, and the chlorine resistance of cellulose acetate benzoate (Reference Example 2) having the same acetyl group substitution degree (2.44) was 24 days. It was inferior to. Industrial applicability
  • the hollow fiber membrane of the present invention can be used as a membrane used in water purification facilities, seawater desalination facilities, sewage treatment facilities, and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention fournit une membrane semi-perméable présentant une résistance au chlore élevée. Plus précisément, l'invention concerne une membrane semi-perméable qui est constituée d'un ester de cellulose. Ledit ester de cellulose possède un groupe benzoyle éventuellement substitué.
PCT/JP2017/011922 2016-04-08 2017-03-24 Membrane semi-perméable WO2017175600A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP17778979.9A EP3441133B1 (fr) 2016-04-08 2017-03-24 Membrane semi-perméable
CN201780022383.4A CN108883379B (zh) 2016-04-08 2017-03-24 半透膜
KR1020187028433A KR102229836B1 (ko) 2016-04-08 2017-03-24 반투막
JP2018510298A JP6981965B2 (ja) 2016-04-08 2017-03-24 半透膜
US16/091,728 US10926230B2 (en) 2016-04-08 2017-03-24 Semipermeable membrane

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016078342 2016-04-08
JP2016-078342 2016-04-08
JP2017-042753 2017-03-07
JP2017042753 2017-03-07

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WO2017175600A1 true WO2017175600A1 (fr) 2017-10-12

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US (1) US10926230B2 (fr)
EP (1) EP3441133B1 (fr)
JP (1) JP6981965B2 (fr)
KR (1) KR102229836B1 (fr)
CN (1) CN108883379B (fr)
WO (1) WO2017175600A1 (fr)

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JP2019198816A (ja) * 2018-05-15 2019-11-21 株式会社ダイセル 半透膜
JP2019217461A (ja) * 2018-06-20 2019-12-26 株式会社ダイセル 中空糸膜
JP2020019854A (ja) * 2018-07-31 2020-02-06 株式会社ダイセル セルロース誘導体とその成形体

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JP7410065B2 (ja) 2020-03-19 2024-01-09 信越化学工業株式会社 生体電極、生体電極の製造方法及び生体信号の測定方法
JP7507136B2 (ja) 2020-11-05 2024-06-27 信越化学工業株式会社 生体電極組成物、生体電極、及び生体電極の製造方法
IL301602A (en) 2021-03-12 2023-05-01 Shinetsu Chemical Co A bio-electrode, a method for producing a bio-electrode, and a method for measuring biological signals
JP2022164579A (ja) 2021-04-16 2022-10-27 信越化学工業株式会社 生体電極組成物、生体電極、及び生体電極の製造方法

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JP2019217461A (ja) * 2018-06-20 2019-12-26 株式会社ダイセル 中空糸膜
JP2020019854A (ja) * 2018-07-31 2020-02-06 株式会社ダイセル セルロース誘導体とその成形体

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EP3441133A1 (fr) 2019-02-13
CN108883379B (zh) 2022-04-05
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EP3441133A4 (fr) 2019-12-04
US10926230B2 (en) 2021-02-23
JP6981965B2 (ja) 2021-12-17
KR20180126496A (ko) 2018-11-27
CN108883379A (zh) 2018-11-23
KR102229836B1 (ko) 2021-03-22
US20190151806A1 (en) 2019-05-23

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